Water-containing glass-based articles with high indentation cracking threshold

ABSTRACT

Glass-based articles that include a hydrogen-containing layer extending from the surface of the article to a depth of layer. The hydrogen-containing layer includes a hydrogen concentration that decreases from a maximum hydrogen concentration to the depth of layer. The glass-based articles exhibit a high Vickers indentation cracking threshold. Glass compositions that are selected to promote the formation of the hydrogen-containing layer and methods of forming the glass-based article are also provided.

BACKGROUND Related Applications

This Application is a continuation of U.S. application Ser. No.17/838,404 filed Jun. 13, 2022, which is a continuation of U.S.application Ser. No. 17/533,506 filed Nov. 23, 2021 which issued on Jul.5, 2022 as U.S. application Ser. No. 11,377,386, which is a continuationof U.S. application Ser. No. 16/193,210 filed Nov. 16, 2018, whichissued on Jan. 4, 2022 as U.S. Pat. No. 11,214,510 and which claims thepriority benefit of U.S. application Ser. No. 62/587,872 filed Nov. 17,2017, each of which is incorporated by reference herein in its entirety.

Field

This disclosure relates to glass-based articles that contain hydrogen,glass compositions utilized to form the glass-based articles, andmethods of forming the glass-based articles.

Technical Background

Portable electronic devices, such as, smartphones, tablets, and wearabledevices (such as, for example, watches and fitness trackers) continue toget smaller and more complex. As such, materials that are conventionallyused on at least one external surface of such portable electronicdevices also continue to get more complex. For instance, as portableelectronic devices get smaller and thinner to meet consumer demand, thedisplay covers and housings used in these portable electronic devicesalso get smaller and thinner, resulting in higher performancerequirements for the materials used to form these components.

Accordingly, a need exists for materials that exhibit higherperformance, such as resistance to damage, for use in portableelectronic devices.

SUMMARY

In aspect (1), a glass-based article is provided. The glass-basedarticle comprises: SiO₂, Al₂O₃, and P₂O₅; and a hydrogen-containinglayer extending from a surface of the glass-based article to a depth oflayer. A hydrogen concentration of the hydrogen-containing layerdecreases from a maximum hydrogen concentration to the depth of layer,and the depth of layer is greater than 5 μm.

In aspect (2), the glass-based article of aspect (1) is provided,wherein the glass-based article has a Vicker's crack initiationthreshold of greater than or equal to 1 kgf.

In aspect (3), the glass-based article of aspect (1) or (2) is provided,wherein the depth of layer is greater than or equal to 10 μm.

In aspect (4), the glass-based article of any of aspects (1) to (3) isprovided, wherein the maximum hydrogen concentration is located at thesurface of the glass-based article.

In aspect (5), the glass-based article of any of aspects (1) to (4) isprovided, further comprising at least one of Li₂O, Na₂O, K₂O, Cs₂O, andRb₂O.

In aspect (6), the glass-based article of any of aspects (1) to (5) isprovided, further comprising K₂O.

In aspect (7), the glass-based article of any of aspects (1) to (6) isprovided, wherein the center of the glass-based article comprises:greater than or equal to 45 mol % to less than or equal to 75 mol %SiO₂; greater than or equal to 3 mol % to less than or equal to 20 mol %Al₂O₃; greater than or equal to 6 mol % to less than or equal to 15 mol% P₂O₅; and greater than or equal to 6 mol % to less than or equal to 25mol % K₂O.

In aspect (8), the glass-based article of any of aspects (1) to (6) isprovided, wherein the center of the glass-based article comprises:greater than or equal to 45 mol % to less than or equal to 75 mol %SiO₂; greater than or equal to 3 mol % to less than or equal to 20 mol %Al₂O₃; greater than or equal to 4 mol % to less than or equal to 15 mol% P₂O₅; and greater than or equal to 11 mol % to less than or equal to25 mol % K₂O.

In aspect (9), the glass-based article of any of aspects (1) to (6) isprovided, wherein the center of the glass-based article comprises:greater than or equal to 55 mol % to less than or equal to 69 mol %SiO₂; greater than or equal to 5 mol % to less than or equal to 15 mol %Al₂O₃; greater than or equal to 6 mol % to less than or equal to 10 mol% P₂O₅; and greater than or equal to 10 mol % to less than or equal to20 mol % K₂O.

In aspect (10), the glass-based article of any of aspects (7) to (9) isprovided, wherein the center of the glass-based article comprises:greater than or equal to 0 mol % to less than or equal to 10 mol % Cs₂O;and greater than or equal to 0 mol % to less than or equal to 10 mol %Rb₂O.

In aspect (11), the glass-based article of any of aspects (1) to (10) isprovided, wherein the glass-based article is substantially free of atleast one of lithium and sodium.

In aspect (12), the glass-based article of any of aspects (1) to (11) isprovided, further comprising a compressive stress layer extending from asurface of the glass-based article into the glass-based article to adepth of compression.

In aspect (13), the glass-based article of aspect (12) is provided,wherein the compressive stress layer comprises a compressive stress ofat least about 100 MPa and the depth of compression is at least about 75μm.

In aspect (14), a consumer electronic product is provided. The consumerelectronic product comprises: a housing comprising a front surface, aback surface and side surfaces; electrical components at least partiallywithin the housing, the electrical components comprising at least acontroller, a memory, and a display, the display at or adjacent thefront surface of the housing; and a cover substrate disposed over thedisplay. At least a portion of at least one of the housing or the coversubstrate comprises the glass-based article of any of aspects (1) to(13).

In aspect (15), a glass is provided. The glass comprises: greater thanor equal to 45 mol % to less than or equal to 75 mol % SiO₂; greaterthan or equal to 3 mol % to less than or equal to 20 mol % Al₂O₃;greater than or equal to 6 mol % to less than or equal to 15 mol % P₂O₅;and greater than or equal to 6 mol % to less than or equal to 25 mol %K₂O.

In aspect (16), the glass of aspect (15) is provided, comprising:greater than or equal to 55 mol % to less than or equal to 69 mol %SiO₂; greater than or equal to 5 mol % to less than or equal to 15 mol %Al₂O₃; greater than or equal to 6 mol % to less than or equal to 10 mol% P₂O₅; and greater than or equal to 10 mol % to less than or equal to20 mol % K₂O.

In aspect (17), the glass of aspect (15) or (16) is provided, furthercomprising: greater than or equal to 0 mol % to less than or equal to 10mol % Cs₂O; and greater than or equal to 0 mol % to less than or equalto 10 mol % Rb₂O.

In aspect (18), the glass of any of aspects (15) to (17) is provided,wherein the glass is substantially free of lithium.

In aspect (19), the glass of any of aspects (15) to (18) is provided,wherein the glass is substantially free of sodium.

In aspect (20), the glass of any of aspects (15) to (19) is provided,comprising: greater than or equal to 58 mol % to less than or equal to63 mol % SiO₂; greater than or equal to 7 mol % to less than or equal to14 mol % Al₂O₃; greater than or equal to 7 mol % to less than or equalto 10 mol % P₂O₅; and greater than or equal to 15 mol % to less than orequal to 20 mol % K₂O.

In aspect (21), the glass of any of aspects (15) to (20) is provided,wherein the glass has a Vicker's crack initiation threshold of greaterthan or equal to 5 kgf.

In aspect (22), the glass of any of aspects (15) to (21) is provided,further comprising at least one of Li₂O, Na₂O, Cs₂O, and Rb₂O.

In aspect (23), a glass is provided. The glass comprises: greater thanor equal to 45 mol % to less than or equal to 75 mol % SiO₂; greaterthan or equal to 3 mol % to less than or equal to 20 mol % Al₂O₃;greater than or equal to 4 mol % to less than or equal to 15 mol % P₂O₅;and greater than or equal to 11 mol % to less than or equal to 25 mol %K₂O.

In aspect (24), the glass of aspect (23) is provided, comprising:greater than or equal to 55 mol % to less than or equal to 69 mol %SiO₂; greater than or equal to 5 mol % to less than or equal to 15 mol %Al₂O₃; greater than or equal to 5 mol % to less than or equal to 10 mol% P₂O₅; and greater than or equal to 11 mol % to less than or equal to20 mol % K₂O.

In aspect (25), the glass of aspect (23) or (24) is provided, furthercomprising: greater than or equal to 0 mol % to less than or equal to 10mol % Cs₂O; and greater than or equal to 0 mol % to less than or equalto 10 mol % Rb₂O.

In aspect (26), the glass of any of aspects (23) to (25) is provided,wherein the glass is substantially free of lithium.

In aspect (27), the glass of any of aspects (23) to (26) is provided,wherein the glass is substantially free of sodium.

In aspect (28), the glass of any of aspects (23) to (27) is provided,comprising: greater than or equal to 58 mol % to less than or equal to63 mol % SiO₂; greater than or equal to 7 mol % to less than or equal to14 mol % Al₂O₃; greater than or equal to 7 mol % to less than or equalto 10 mol % P₂O₅; and greater than or equal to 15 mol % to less than orequal to 20 mol % K₂O.

In aspect (29), the glass of any of aspects (23) to (28) is provided,wherein the glass has a Vicker's crack initiation threshold of greaterthan or equal to 5 kgf.

In aspect (30), the glass of any of aspects (23) to (29) is provided,further comprising at least one of Li₂O, Na₂O, Cs₂O, and Rb₂O.

In aspect (31), a method is provided. The method comprises: exposing aglass-based substrate to an environment with a relative humidity ofgreater than or equal to 75% to form glass-based article with ahydrogen-containing layer extending from a surface of the glass-basedarticle to a depth of layer. The glass-based substrate includes SiO₂,Al₂O₃, and P₂O₅. A hydrogen concentration of the hydrogen-containinglayer decreases from a maximum hydrogen concentration to the depth oflayer, and the depth of layer is greater than 5 μm.

In aspect (32), the method of aspect (31) is provided, wherein theglass-based substrate has a composition comprising: greater than orequal to 55 mol % to less than or equal to 69 mol % SiO₂; greater thanor equal to 5 mol % to less than or equal to 15 mol % Al₂O₃; greaterthan or equal to 6 mol % to less than or equal to 10 mol % P₂O₅; andgreater than or equal to 10 mol % to less than or equal to 20 mol % K₂O.

In aspect (33), the method of aspect (31) is provided, wherein theglass-based substrate has a composition comprising: greater than orequal to 45 mol % to less than or equal to 75 mol % SiO₂; greater thanor equal to 3 mol % to less than or equal to 20 mol % Al₂O₃; greaterthan or equal to 4 mol % to less than or equal to 15 mol % P₂O₅; andgreater than or equal to 11 mol % to less than or equal to 25 mol % K₂O.

In aspect (34), the method of aspect (31) is provided, wherein theglass-based substrate has a composition comprising: greater than orequal to 45 mol % to less than or equal to 75 mol % SiO₂; greater thanor equal to 3 mol % to less than or equal to 20 mol % Al₂O₃; greaterthan or equal to 6 mol % to less than or equal to 15 mol % P₂O₅; andgreater than or equal to 6 mol % to less than or equal to 25 mol % K₂O.

In aspect (35), the method of any of aspects (31) to (34) is provided,wherein the glass-based substrate further comprises: greater than orequal to 0 mol % to less than or equal t10 mol % Cs₂O; and greater thanor equal to 0 mol % to less than or equal t10 mol % Rb₂O.

In aspect (36), the method of any of aspects (31) to (35) is provided,further comprising at least one of Li₂O, Na₂O, Cs₂O, and Rb₂O.

In aspect (37), the method of any of aspects (31) to (36) is provided,wherein the glass-based substrate is substantially free of at least oneof lithium and sodium.

In aspect (38), the method of any of aspects (31) to (37) is provided,wherein the exposing takes place at a temperature of greater than orequal to 70° C.

In aspect (39), the method of any of aspects (31) to (3 8) is provided,wherein the glass-based article has a Vicker's crack initiationthreshold of greater than or equal to 1 kgf.

These and other aspects, advantages, and salient features will becomeapparent from the following detailed description, the accompanyingdrawings, and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a representation of a cross-section of a glass-based articleaccording to an embodiment.

FIG. 2A is a plan view of an exemplary electronic device incorporatingany of the glass-based articles disclosed herein.

FIG. 2B is a perspective view of the exemplary electronic device of FIG.2A.

FIG. 3 is a measurement of hydrogen concentration as a function of depthbelow the surface produced by SIMS for a glass-based article formed froma glass-based substrate having a composition of Example 1.

FIG. 4 is a photograph of a Vickers indent at 5 kgf in a glass-basedsubstrate having the composition of Example 1 prior to exposure to awater containing environment.

FIG. 5 is a photograph of a Vickers indent at 10 kgf in a glass-basedsubstrate having the composition of Example 1 prior to exposure to awater containing environment.

FIG. 6 is a photograph of a Vickers indent at 5 kgf in a glass-basedarticle formed by exposing a glass-based substrate having thecomposition of Example 1 to a water containing environment.

FIG. 7 is a photograph of a Vickers indent at 10 kgf in a glass-basedarticle formed by exposing a glass-based substrate having thecomposition of Example 1 to a water containing environment.

FIG. 8 is a photograph of a Vickers indent at 20 kgf in a glass-basedarticle formed by exposing a glass-based substrate having thecomposition of Example 1 to a water containing environment.

FIG. 9 is a plot of the hydroxyl (BOH) concentration of a 0.5 mm thickglass article as a function of depth from the surface after exposure toa water containing environment according to an embodiment.

FIG. 10 is a plot of the hydroxyl (BOH) concentration of a 1.0 mm thickglass article as a function of depth from the surface after exposure toa water containing environment according to an embodiment.

FIG. 11 is a side view of a ring-on-ring test apparatus.

DETAILED DESCRIPTION

In the following description, like reference characters designate likeor corresponding parts throughout the several views shown in thefigures. It is also understood that, unless otherwise specified, termssuch as “top,” “bottom,” “outward,” “inward,” and the like are words ofconvenience and are not to be construed as limiting terms. Unlessotherwise specified, a range of values, when recited, includes both theupper and lower limits of the range as well as any sub-rangestherebetween. As used herein, the indefinite articles “a,” “an,” and thecorresponding definite article “the” mean “at least one” or “one ormore,” unless otherwise specified. It also is understood that thevarious features disclosed in the specification and the drawings can beused in any and all combinations.

As used herein, the term “glass-based” is used in its broadest sense toinclude any objects made wholly or partly of glass, including glassceramics (which include a crystalline phase and a residual amorphousglass phase). Unless otherwise specified, all compositions of theglasses described herein are expressed in terms of mole percent (mol %),and the constituents are provided on an oxide basis. Unless otherwisespecified, all temperatures are expressed in terms of degrees Celsius (°C.).

It is noted that the terms “substantially” and “about” may be utilizedherein to represent the inherent degree of uncertainty that may beattributed to any quantitative comparison, value, measurement, or otherrepresentation. These terms are also utilized herein to represent thedegree by which a quantitative representation may vary from a statedreference without resulting in a change in the basic function of thesubject matter at issue. For example, a glass that is “substantiallyfree of K₂O” is one in which K₂O is not actively added or batched intothe glass, but may be present in very small amounts as a contaminant,such as in amounts of less than about 0.01 mol %. As utilized herein,when the term “about” is used to modify a value, the exact value is alsodisclosed. For example, the term “greater than about 10 mol %” alsodiscloses “greater than or equal to 10 mol %.”

Reference will now be made in detail to various embodiments, examples ofwhich are illustrated in the accompanying examples and drawings.

The glass-based articles disclosed herein include a hydrogen-containinglayer extending from a surface of the article to a depth of layer. Thehydrogen-containing layer includes a hydrogen concentration thatdecreases from a maximum hydrogen concentration of the glass-basedarticle to the depth of layer. In some embodiments, the maximum hydrogenconcentration may be located at the surface of the glass-based article.The glass-based articles exhibit a high Vickers indentation crackingthreshold (e.g., greater than or equal to 1 kgf), without the use oftraditional stengthening methods (for example, ion-exchange of a pair ofalkali ions or thermal tempering). The high Vickers indentation crackingthresholds exhibited by the glass-based articles signify a highresistance to damage.

The glass-based articles may be formed by exposing glass-basedsubstrates to environments containing water vapor, thereby allowinghydrogen species to penetrate the glass-based substrates and form theglass-based articles having a hydrogen-containing layer. As utilizedherein, hydrogen species includes molecular water, hydroxyl, hydrogenions, and hydronium. The composition of the glass-based substrates maybe selected to promote the interdiffusion of hydrogen species into theglass. As utilized herein, the term “glass-based substrate” refers tothe precursor prior to exposure to a water vapor containing environmentfor the formation of a glass-based article that includeshydrogen-containing layers. Similarly, the term “glass-based article”refers to the post exposure article that includes a hydrogen-containinglayer.

A representative cross-section of a glass-based article 100 according tosome embodiments is depicted in FIG. 1 . The glass-based article 100 hasa thickness t that extends between a first surface 110 and a secondsurface 112. A first hydrogen-containing layer 120 extends from thefirst surface 110 to a first depth of layer, where the first depth oflayer has a depth d₁ measured from the first surface 110 into theglass-based article 100. A second hydrogen-containing layer 122 extendsfrom the second surface 112 to a second depth of layer, where the seconddepth of layer has a depth d₂ measured from the second surface 112 intothe glass-based article 100. An added-hydrogen-species free region 130is present between the first depth of layer and the second depth oflayer.

The hydrogen-containing layer of the glass-based articles may have adepth of layer (DOL) greater than 5 μm. In some embodiments, the depthof layer may be greater than or equal to 10 μm, such as greater than orequal to 15 μm, greater than or equal to 20 μm, greater than or equal to25 μm, greater than or equal to 30 μm, greater than or equal to 35 μm,greater than or equal to 40 μm, greater than or equal to 45 μm, greaterthan or equal to 50 μm, greater than or equal to 55 μm, greater than orequal to 60 μm, greater than or equal to 65 μm, greater than or equal to70 μm, greater than or equal to 75 μm, greater than or equal to 80 μm,greater than or equal to 85 μm, greater than or equal to 90 μm, greaterthan or equal to 95 μm, greater than or equal to 100 μm, greater than orequal to 105 μm, greater than or equal to 110 μm, greater than or equalto 115 μm, greater than or equal to 120 μm, greater than or equal to 125μm, greater than or equal to 130 μm, greater than or equal to 135 μm,greater than or equal to 140 μm, greater than or equal to 145 μm,greater than or equal to 150 μm, greater than or equal to 155 μm,greater than or equal to 160 μm, greater than or equal to 165 μm,greater than or equal to 170 μm, greater than or equal to 175 μm,greater than or equal to 180 μm, greater than or equal to 185 μm,greater than or equal to 190 μm, greater than or equal to 195 μm,greater than or equal to 200 μm, or more. In some embodiments, the depthof layer may be from greater than 5 μm to less than or equal to 205 μm,such as from greater than or equal to 10 μm to less than or equal to 200μm, from greater than or equal to 15 μm to less than or equal to 200 μm,from greater than or equal to 20 μm to less than or equal to 195 μm,from greater than or equal to 25 μm to less than or equal to 190 μm,from greater than or equal to 30 μm to less than or equal to 185 μm,from greater than or equal to 35 μm to less than or equal to 180 μm,from greater than or equal to 40 μm to less than or equal to 175 μm,from greater than or equal to 45 μm to less than or equal to 170 μm,from greater than or equal to 50 μm to less than or equal to 165 μm,from greater than or equal to 55 μm to less than or equal to 160 μm,from greater than or equal to 60 μm to less than or equal to 155 μm,from greater than or equal to 65 μm to less than or equal to 150 μm,from greater than or equal to 70 μm to less than or equal to 145 μm,from greater than or equal to 75 μm to less than or equal to 140 μm,from greater than or equal to 80 μm to less than or equal to 135 μm,from greater than or equal to 85 μm to less than or equal to 130 μm,from greater than or equal to 90 μm to less than or equal to 125 μm,from greater than or equal to 95 μm to less than or equal to 120 μm,from greater than or equal to 100 μm to less than or equal to 115 μm,from greater than or equal to 105 μm to less than or equal to 110 μm, orany sub-ranges formed by any of these endpoints. In general, the depthof layer exhibited by the glass-based articles is greater than the depthof layer that may be produced by exposure to the ambient environment.

The hydrogen-containing layer of the glass-based articles may have adepth of layer (DOL) greater than 0.005 t, wherein t is the thickness ofthe glass-based article. In some embodiments, the depth of layer may begreater than or equal to 0.010 t, such as greater than or equal to 0.015t, greater than or equal to 0.020 t, greater than or equal to 0.025 t,greater than or equal to 0.03 0 t, greater than or equal to 0.035 t,greater than or equal to 0.040 t, greater than or equal to 0.045 t,greater than or equal to 0.050 t, greater than or equal to 0.055 t,greater than or equal to 0.060 t, greater than or equal to 0.065 t,greater than or equal to 0.070 t, greater than or equal to 0.075 t,greater than or equal to 0.080 t, greater than or equal to 0.085 t,greater than or equal to 0.090 t, greater than or equal to 0.095 t,greater than or equal to 0.10 t, greater than or equal to 0.15 t,greater than or equal to 0.20 t, or more. In some embodiments, the DOLmay be from greater than 0.005 t to less than or equal to 0.205 t, suchas from greater than or equal to 0.010 t to less than or equal to 0.200t, from greater than or equal to 0.015 t to less than or equal to 0.195t, from greater than or equal to 0.020 t to less than or equal to 0.190t, from greater than or equal to 0.025 t to less than or equal to 0.185t, from greater than or equal to 0.030 t to less than or equal to 0.180t, from greater than or equal to 0.035 t to less than or equal to 0.175t, from greater than or equal to 0.040 t to less than or equal to 0.170t, from greater than or equal to 0.045 t to less than or equal to 0.165t, from greater than or equal to 0.050 t to less than or equal to 0.160t, from greater than or equal to 0.055 t to less than or equal to 0.155t, from greater than or equal to 0.060 t to less than or equal to 0.150t, from greater than or equal to 0.065 t to less than or equal to 0.145t, from greater than or equal to 0.070 t to less than or equal to 0.140t, from greater than or equal to 0.075 t to less than or equal to 0.135t, from greater than or equal to 0.080 t to less than or equal to 0.130t, from greater than or equal to 0.085 t to less than or equal to 0.125t, from greater than or equal to 0.090 t to less than or equal to 0.120t, from greater than or equal to 0.095 t to less than or equal to 0.115t, from greater than or equal to 0.100 t to less than or equal to 0.110t, or any sub-ranges formed by any of these endpoints.

The depth of layer and hydrogen concentration are measured by asecondary ion mass spectrometry (SIMS) technique that is known in theart. The SIMS technique is capable of measuring the hydrogenconcentration at a given depth, but is not capable of distinguishing thehydrogen species present in the glass-based article. For this reason,all hydrogen species contribute to the SIMS measured hydrogenconcentration. As utilized herein, the depth of layer (DOL) refers tothe first depth below the surface of the glass-based article where thehydrogen concentration is equal to the hydrogen concentration at thecenter of the glass-based article. This definition accounts for thehydrogen concentration of the glass-based substrate prior to treatment,such that the depth of layer refers to the depth of the hydrogen addedby the treatment process. As a practical matter, the hydrogenconcentration at the center of the glass-based article may beapproximated by the hydrogen concentration at the depth from the surfaceof the glass-based article where the hydrogen concentration becomessubstantially constant, as the hydrogen concentration is not expected tochange between such a depth and the center of the glass-based article.This approximation allows for the determination of the DOL withoutmeasuring the hydrogen concentration throughout the entire depth of theglass-based article.

In some embodiments, the entirety of the thickness of the glass-basedarticle may be part of a hydrogen-containing layer. Such a glass-basedarticle may be produced when the treatment of a glass-based substrateextends for a sufficient time in sufficient conditions for hydrogenspecies to diffuse to the center of the glass-based article from eachexposed surface. In some embodiments, where the surfaces of theglass-based article are exposed to the same treatment conditions aminimum hydrogen concentrationj may be located at half the thickness ofthe glass-based article, such that the hydrogen-containing layers meetat the center of the glass-based article. In such embodiments, the DOLmay be located at half the thickness of the glass-based articles. Insome embodiments, the glass-based articles may not include a region thatis free of added hydrogen species. In some embodiments, the glass-basedarticles may be treated in a humid environment such that theconcentration of the added hydrogen species equilibriates throughout theglass-based articles, and the hydrogen concentration does not vary withdepth below the surface of the glass-based article. The glass-basedarticles according to such embodiments would not exhibit a DOL asdefined herein, as the hydrogen concentration at the center of theglass-based article would be equivalent to the hydrogen concentration atall other depths.

The glass-based articles are highly resistant to Vickers indentationcracking. The high Vickers indentation cracking resistance imparts ahigh damage resistance to the glass-based articles. Without wishing tobe bound by any particular theory, the water content of the glass-basedarticles may reduce the local viscosity of the hydrogen-containing layersuch that local flow occurs instead of cracking. The Vickers indentationcracking threshold of the glass-based articles is achieved without theuse of conventional strengthening techniques, such as the exchange oflarge alkali ions for smaller alkali ions in the glass, thermaltempering, or lamination of glass layers with a coefficient of thermalexpansion mismatch. The glass-based articles exhibit a Vickersindentation cracking threshold of greater than or equal to 1 kgf, suchas greater than or equal to 2 kgf, greater than or equal to 3 kgf,greater than or equal to 4 kgf, greater than or equal to 5 kgf, greaterthan or equal to 6 kgf, greater than or equal to 7 kgf, greater than orequal to 8 kgf, greater than or equal to 9 kgf, greater than or equal to10 kgf, greater than or equal to 11 kgf, greater than or equal to 12kgf, greater than or equal to 13 kgf, greater than or equal to 14 kgf,greater than or equal to 15 kgf, greater than or equal to 16 kgf,greater than or equal to 17 kgf, greater than or equal to 18 kgf,greater than or equal to 19 kgf, greater than or equal to 20 kgf,greater than or equal to 21 kgf, greater than or equal to 22 kgf,greater than or equal to 23 kgf, greater than or equal to 24 kgf,greater than or equal to 25 kgf, greater than or equal to 26 kgf,greater than or equal to 27 kgf, greater than or equal to 28 kgf,greater than or equal to 29 kgf, greater than or equal to 30 kgf, ormore. In some embodiments, the glass-based articles exhibit a Vickersindentation cracking threshold from greater than or equal to 1 kgf toless than or equal to 30 kgf, such as from greater than or equal to 2kgf to less than or equal to 29 kgf, from greater than or equal to 3 kgfto less than or equal to 28 kgf, from greater than or equal to 4 kgf toless than or equal to 27 kgf, from greater than or equal to 5 kgf toless than or equal to 26 kgf, from greater than or equal to 6kgf to lessthan or equal to 25 kgf, from greater than or equal to 7 kgf to lessthan or equal to 24 kgf, from greater than or equal to 8 kgf to lessthan or equal to 23 kgf, from greater than or equal to 9 kgf to lessthan or equal to 22 kgf, from greater than or equal to 10 kgf to lessthan or equal to 21 kgf, from greater than or equal to 11 kgf to lessthan or equal to 20 kgf, from greater than or equal to 12 kgf to lessthan or equal to 19 kgf, from greater than or equal to 13 kgf to lessthan or equal to 18 kgf, from greater than or equal to 14 kgf to lessthan or equal to 17 kgf, from greater than or equal to 15 kgf to lessthan or equal to 16 kgf, or any sub-ranges formed by any of theseendpoints.

Vickers crack initiation threshold (or Indentation Fracture Threshold)was measured by a Vickers indenter. Vickers crack initiation thresholdis a measure of indentation damage resistance of the glass. The testinvolved the use of a square-based pyramidal diamond indenter with anangle of 136° between faces, referred to as a Vickers indenter. TheVickers indenter was the same as the one used in standard micro hardnesstesting (as described in ASTM-E384-11). A minimum of five specimens werechosen to represent the glass type and/or sample of interest. For eachspecimen, multiple sets of five indentations were introduced to thespecimen surface. Each set of five indentations was introduced at agiven load, with each individual indentation separated by a minimum of 5mm and no closer than 5 mm to a specimen edge. A rate of indenterloading/unloading of 50 kg/minute was used for test loads≥2 kg. For testloads<2 kg, a rate of 5 kg/minute was used. A dwell (i.e., hold) time of10 seconds at the target load was utilized. The machine maintained loadcontrol during the dwell period. After a period of at least 12 hours,the indentations were inspected under reflected light using a compoundmicroscope at 500× magnification. The presence or absence ofmedian/radial cracks (cracks extending from the indentation along aplane perpendicular to the major plane of the article), or specimenfracture, was then noted for each indentation. Note that the formationof lateral cracks (cracks extending along a plane parallel to the majorplane of the article) was not considered indicative of exhibitingthreshold behavior, since the formation of median/radial cracks was ofinterest, or specimen fracture, for this test. The specimen thresholdvalue is defined as the midpoint of the lowest consecutive indentationloads which bracket greater than 50% of the individual indentationsmeeting threshold. For example, if within an individual specimen, 2 ofthe 5 (40%) indentations induced at a 5 kg load have exceeded threshold,and 3 of the 5 (60%) indentations induced at a 6 kg load have exceededthreshold, then the specimen threshold value would be defined as greaterthan 5 kg. The range (lowest value to highest value) of all the specimenmidpoints may also be reported for each sample. The pre-test, test andpost-test environment was controlled to 23±2° C. and 50±5% RH tominimize variation in the fatigue (stress corrosion) behavior of thespecimens.

Without wishing to be bound by any particular theory, thehydrogen-containing layer of the glass-based articles may be the resultof an interdiffusion of hydrogen species for ions contained in thecompositions of the glass-based substrate. Monovalenthydrogen-containing species, such as H₃O⁺ and/or H⁺, may replace alkaliions contained in the glass-based substrate composition to form theglass-based article. The size of the alkali ions that thehydrogen-containing species replaces contributes to the diffusivity ofthe hydrogen-containing species in the glass-based substrate, as largeralkali ions produce larger interstitial spaces that facilitate theinterdiffusion mechanism. For example, the hydronium ion (H₃O⁺) has anionic radius that is close to the ionic radius of potassium, and muchlarger than the ionic radius of lithium. It was observed that thediffusivity of the hydrogen-containing species in the glass-basedsubstrate is significantly higher, by two orderes of magnitude, when theglass-based substrate contains potassium than when the glass-basedsubstrate contains lithium. This observed behavior may also indicatethat the hydronium ion is the primary monovalent hydrogen-containingspecies that diffuses into the glass-based substrate. The ionic radiifor the alkali ions and the hydronium ion are reported in Table I below.As shown in Table I, rubidium and cesium have ionic radii that aresignificantly larger than the hydronium ion, which may result in higherhydrogen diffusivities than those observed for potassium.

TABLE I Ion Radius (nm) Lithium 0.059 Sodium 0.099 Potassium 0.133Hydronium 0.137 Rubidium 0.152 Cesium 0.167

In some embodiments, the replacement of alkali ions in the glass-basedsubstrate with the hydrogen-containing ions may produce a compressivestress layer extending from the surface of the glass-basd article intothe glass-based article to a depth of compression. As used herein, depthof compression (DOC) means the depth at which the stress in theglass-based article changes from compressive to tensile. Thus, theglass-based article also contains a tensile stress region having amaximum central tension (CT), such that the forces within theglass-based article are balanced. Without wishing to be bound by anytheory, the compressive stress region may be the result of the exchangeof hydrogen-containing ions with an ionic radius that is larger than theions which they replace.

In some embodiments, the compressive stress layer may include acompressive stress of at greater than or equal to 100 MPa, such asgreater than or equal to 105 MPa, greater than or equal to 110 MPa,greater than or equal to 115 MPa, greater than or equal to 120 MPa,greater than or equal to 125 MPa, greater than or equal to 130 MPa, abogreater than or equal to ut 135 MPa, or more. In some embodiments, thecompressive stress layer may include a compressive stress of fromgreater than or equal to 100 MPa to less than or equal to 150 MPa, suchas from greater than or equal to 105 MPa to less than or equal to 145MPa, from greater than or equal to 110 MPa to less than or equal to 140MPa, from greater than or equal to 115 MPa to less than or equal to 135MPa, from greater than or equal to 120 MPa to less than or equal to 130MPa, 125 MPa, or any sub-ranges formed from any of these endpoints.

In some embodiments, the DOC of the compressive stress layer may begreater than or equal to 75 μm, such as greater than or equal to 80 μm,greater than or equal to 85 μm, greater than or equal to 90 μm, greaterthan or equal to 95 μm, greater than or equal to 100 μm, or more. Insome embodiments, the DOC of the compressive stress layer may be at fromgreater than or equal to 75 μm to less than or equal to 115 μm, such asfrom greater than or equal to 80 μm to less than or equal to 110 μm,from greater than or equal to 85 μm to less than or equal to 105 μm,from greater than or equal to 90 μm to less than or equal to 100 μm, 95μm, or any sub-ranges that may be formed from any of these endpoints.

In some embodiments, the glass-based articles may have a DOC greaterthan or equal to 0.05 t, wherein tis the thickness of the glass-basedarticle, such as greater than or equal to 0.06 t, greater than or equalto 0.07 t, greater than or equal to 0.08 t, greater than or equal to0.09 t, greater than or equal to 0.10 t, greater than or equal to 0.11t, greater than or equal to 0.12 t, or more. In some embodiments, theglass-based articles may have a DOC from greater than or equal to 0.05 tto less than or equal to 0.20 t, such as from greater than or equal to0.06 t to less than or equal to 0.19 t, from greater than or equal to0.07 t to less than or equal to 0.18 t, from greater than or equal to0.08 t to less than or equal to 0.17 t, from greater than or equal to0.09 t to less than or equal to 0.16 t, from greater than or equal to0.10 t to less than or equal to 0.15 t, from greater than or equal to0.11 t to less than or equal to 0.14 t, from greater than or equal to0.12 t to less than or equal to 0.13 t, or any sub-ranges formed fromany of these endpoints.

In some embodiments, the CT of the glass-based article may be greaterthan or equal to 10 MPa, such as greater than or equal to 11 MPa,greater than or equal to 12 MPa, greater than or equal to 13 MPa,greater than or equal to 14 MPa, greater than or equal to 15 MPa,greater than or equal to 16 MPa, greater than or equal to 17 MPa,greater than or equal to 18 MPa, greater than or equal to 19 MPa,greater than or equal to 20 MPa, greater than or equal to 22 MPa,greater than or equal to 24 MPa, greater than or equal to 26 MPa,greater than or equal to 28 MPa, greater than or equal to 30 MPa,greater than or equal to 32 MPa, or more. In some embodiments, the CT ofthe glass-based article may be from greater than or equal to 10 MPa toless than or equal to 35 MPa, such as from greater than or equal to 11MPa to less than or equal to 34 MPa, from greater than or equal to 12MPa to less than or equal to 33 MPa, from greater than or equal to 13MPa to less than or equal to 32 MPa, from greater than or equal to 14MPa to less than or equal to 32 MPa, from greater than or equal to 15MPa to less than or equal to 31 MPa, from greater than or equal to 16MPa to less than or equal to 30 MPa, from greater than or equal to 17MPa to less than or equal to 28 MPa, from greater than or equal to 18MPa to less than or equal to 26 MPa, from greater than or equal to 19MPa to less than or equal to 24 MPa, from greater than or equal to 20MPa to less than or equal to 22 MPa, or any sub-ranges formed from anyof these endpoints.

Compressive stress (including surface CS) is measured by surface stressmeter using commercially available instruments such as the FSM-6000(FSM), manufactured by Orihara Industrial Co., Ltd. (Japan). Surfacestress measurements rely upon the accurate measurement of the stressoptical coefficient (SOC), which is related to the birefringence of theglass. SOC in turn is measured according to Procedure C (Glass DiscMethod) described in ASTM standard C770-16, entitled “Standard TestMethod for Measurement of Glass Stress-Optical Coefficient,” thecontents of which are incorporated herein by reference in theirentirety. DOC is measured by FSM. The maximum central tension (CT)values are measured using a scattered light polariscope (SCALP)technique known in the art.

The glass-based articles may be formed from glass-based substrateshaving any appropriate composition. The composition of the glass-basedsubstrate may be specifically selected to promote the diffusion ofhydrogen-containing species, such that a glass-based article including ahydrogen-containing layer may be formed efficiently. In someembodiments, the glass-based substrates may have a composition thatincludes SiO₂, Al₂O₃, and P₂O₅. In some embodiments, the glass-basedsubstrates may additionally include an alkali metal oxide, such as atleast one of Li₂O, Na₂O, K₂O, Rb₂O, and Cs₂O. In some embodiments, theglass-based substrates may be substantially free, or free, of at leastone of lithium and sodium. In some embodiments, after the diffusion ofthe hydrogen-containing species into the glass-based substrate, theglass-based article may have a bulk composition that is approximatelythe same as the composition of the glass-based substrate. In someembodiments, the hydrogen species may not diffuse to the center of theglass-based article. Stated differently, the center of the glass-basedarticle is the area least affected by the water vapor treatment. Forthis reason, the center of the glass-based article may have acomposition that is substantially the same, or the same, as thecomposition of the glass-based substrate prior to treatment in a watercontaining environment.

The glass-based substrate may include any appropriate amount of SiO₂.SiO₂ is the largest constituent and, as such, SiO₂ is the primaryconstituent of the glass network formed from the glass composition. Ifthe concentration of SiO₂ in the glass composition is too high, theformability of the glass composition may be diminished as higherconcentrations of SiO₂ increase the difficulty of melting the glass,which, in turn, adversely impacts the formability of the glass. In someembodiments, the glass-based substrate may include SiO₂ in an amountfrom greater than or equal to 45 mol % to less than or equal to 75 mol%, such as from greater than or equal to 46 mol % to less than or equalto 74 mol %, from greater than or equal to 47 mol % to less than orequal to 73 mol %, from greater than or equal to 48 mol % to less thanor equal to 72 mol %, from greater than or equal to 49 mol % to lessthan or equal to 71 mol %, from greater than or equal to 50 mol % toless than or equal to 70 mol %, from greater than or equal to 51 mol %to less than or equal to 69 mol %, from greater than or equal to 52 mol% to less than or equal to 68 mol %, from greater than or equal to 53mol % to less than or equal to 67 mol %, from greater than or equal to54 mol % to less than or equal to 66 mol %, from greater than or equalto 55 mol % to less than or equal to 65 mol %, from greater than orequal to 56 mol % to less than or equal to 64 mol %, from greater thanor equal to 57 mol % to less than or equal to 63 mol %, from greaterthan or equal to 58 mol % to less than or equal to 62 mol %, fromgreater than or equal to 59 mol % to less than or equal to 61 mol %, 60mol %, or any sub-ranges formed by any of these endpoints. In someembodiments, the glass-based substrate may include SiO₂ in an amountfrom greater than or equal to 55 mol % to less than or equal to 69 mol%, such as from greater than or equal to 58 mol % to less than or equalto 63 mol %, or any sub-ranges formed from any of these endpoints.

The glass-based substrate may include any appropriate amount of Al₂O₃.Al₂O₃ may serve as a glass network former, similar to SiO₂. Al₂O₃ mayincrease the viscosity of the glass composition due to its tetrahedralcoordination in a glass melt formed from a glass composition, decreasingthe formability of the glass composition when the amount of Al₂O₃ is toohigh. However, when the concentration of Al₂O₃ is balanced against theconcentration of SiO₂ and the concentration of alkali oxides in theglass composition, Al₂O₃ can reduce the liquidus temperature of theglass melt, thereby enhancing the liquidus viscosity and improving thecompatibility of the glass composition with certain forming processes,such as the fusion forming process. The inclusion of Al₂O₃ in theglass-based substrate prevents phase separation and reduces the numberof non-bridging oxygens (NBOs) in the glass. Additionally, Al₂O₃ canimprove the effectiveness of ion exchange. In some embodiments, theglass-based substrate may include Al₂O₃ in an amount of from greaterthan or equal to 3 mol % to less than or equal to 20 mol %, such as fromgreater than or equal to 4 mol % to less than or equal to 19 mol %, fromgreater than or equal to 5 mol % to less than or equal to 18 mol %, fromgreater than or equal to 6 mol % to less than or equal to 17 mol %, fromgreater than or equal to 7 mol % to less than or equal to 16 mol %, fromgreater than or equal to 8 mol % to less than or equal to 15 mol %, fromgreater than or equal to 9 mol % to less than or equal to 14 mol %, fromgreater than or equal to 10 mol % to less than or equal to 13 mol %,from greater than or equal to 11 mol % to less than or equal to 12 mol%, or any sub-ranges formed by any of these endpoints. In someembodiments, the glass-based substrate may include Al₂O₃ in an amount offrom greater than or equal to 5 mol % to less than or equal to 15 mol %,such as from greater than or equal to 7 mol % to less than or equal to14 mol %, or any sub-ranges formed from any of these endpoints.

The glass-based substrate may include any amount of P₂O₅ sufficient toproduce the desired hydrogen diffusivity. The inclusion of phosphorousin the glass-based substrate promotes faster interdiffusion, regardlessof the exchanging ionic pair. Thus, the phosphorous containingglass-based substrates allow the efficient formation of glass-basedarticles including a hydrogen-containing layer. The inclusion of P₂O₅also allows for the production of a glass-based article with a deepdepth of layer (e.g., greater than about 10 μm) in a relatively shorttreatment time. In some embodiments, the glass-based substrate mayinclude P₂O₅ in an amount of from greater than or equal to 4 mol % toless than or equal to 15 mol %, such as from greater than or equal to 5mol % to less than or equal to 14 mol %, from greater than or equal to 6mol % to less than or equal to 13 mol %, from greater than or equal to 7mol % to less than or equal to 12 mol %, from greater than or equal to 8mol % to less than or equal to 11 mol %, from greater than or equal to 9mol % to less than or equal to 10 mol %, or any sub-ranges formed by anyof these endpoints. In some embodiments, the glass-based substrate mayinclude P₂O₅ in an amount of from greater than or equal to 5 mol % toless than or equal to 15 mol %, such as from greater than or equal to 6mol % to less than or equal to 15 mol %, from greater than or equal to 5mol % to less than or equal to 10 mol %, from greater than or equal to 6mol % to less than or equal to 10 mol %, from greater than or equal to 7mol % to less than or equal to 10 mol %, or any sub-ranges formed by anyof these endpoints.

The glass-based substrate may include an alkali metal oxide in anyappropriate amount The alkali metal oxides promote ion exchange. The sumof the alkali metal oxides (e.g., Li₂O, Na₂O, and K₂O as well as otheralkali metal oxides including Cs₂O and Rb₂O) in the glass compositionmay be referred to as “R₂O”, and R₂O may be expressed in mol %. In someembodiments, the glass-based substrate may be substrantially free, orfree, of at least one of lithium and sodium. In embodiments, the glasscomposition comprises R₂O in an amount greater than or equal to 6 mol %,such as greater than or equal to 7 mol %, greater than or equal to 8 mol%, greater than or equal to 9 mol %, greater than or equal to 10 mol %,greater than or equal to 11 mol %, greater than or equal to 12 mol %,greater than or equal to 13 mol %, greater than or equal to 14 mol %,greater than or equal to 15 mol %, greater than or equal to 16 mol %,greater than or equal to 17 mol %, greater than or equal to 18 mol %,greater than or equal to 19 mol %, greater than or equal to 20 mol %,greater than or equal to 21 mol %, greater than or equal to 22 mol %,greater than or equal to abut 23 mol %, or greater than or equal to 24mol %. In one or more embodiments, the glass composition comprises R₂Oin an amount less than or equal to 25 mol %, such as less than or equalto 24 mol %, less than or equal to 23 mol %, less than or equal to 22mol %, less than or equal to 21 mol %, less than or equal to 20 mol %,less than or equal to 19 mol %, less than or equal to 18 mol %, lessthan or equal to 17 mol %, less than or equal to 16 mol %, less than orequal to 15 mol %, less than or equal to abut 14 mol %, less than orequal to 13 mol %, less than or equal to 12 mol %, less than or equal to11 mol %, less than or equal to 10 mol %, less than or equal to 9 mol %,less than or equal to 8 mol %, or less than or equal to 7 mol %. Itshould be understood that, in embodiments, any of the above ranges maybe combined with any other range. In some embodiments, the glasscomposition comprises R₂O in an amount from greater than or equal to 6.0mol % to less than or equal to 25.0 mol %, such as from greater than orequal to 7.0 mol % to less than or equal to 24.0 mol %, from greaterthan or equal to 8.0 mol % to less than or equal to 23.0 mol %, fromgreater than or equal to 9.0 mol % to less than or equal to 22.0 mol %,from greater than or equal to 10.0 mol % to less than or equal to 21.0mol %, from greater than or equal to 11.0 mol % to less than or equal to20.0 mol %, from greater than or equal to aout 12.0 mol % to less thanor equal to 19.0 mol %, from greater than or equal to 13.0 mol % to lessthan or equal to 18.0 mol %, from greater than or equal to 14.0 mol % toless than or equal to 17.0 mol %, or from greater than or equal to 15.0mol % to less than or equal to 16.0 mol %, and all ranges and sub-rangesbetween the foregoing values.

In some embodiments, the alkali metal oxide may be K₂O. The inclusion ofK₂O allows the efficient exchange of hydrogen species, into the glasssubstrate upon exposure to a water containing environment. Inembodiments, the glass-based substrate may include K₂O in an amount offrom greater than or equal to 6 mol % to less than or equal to 25 mol %,such as from greater than or equal to 7 mol % to less than or equal to24 mol %, from greater than or equal to 8 mol % to less than or equal to23 mol %, from greater than or equal to 9 mol % to less than or equal to22 mol %, from greater than or equal to 10 mol % to less than or equalto 21 mol %, from greater than or equal to 11 mol % to less than orequal to 20 mol %, from greater than or equal to 12 mol % to less thanor equal to 19 mol %, from greater than or equal to 13 mol % to lessthan or equal to 18 mol %, from greater than or equal to 14 mol % toless than or equal to 17 mol %, from greater than or equal to 15 mol %to less than or equal to 16 mol %, or any sub-ranges formed from any ofthese endpoints. In some embodiments, the glass-based substrate mayinclude K₂O in an amount of from greater than or equal to 10 mol % toless than or equal to 25 mol %, such as from greater than or equal to 10mol % to less than or equal to 20 mol %, from greater than or equal to11 mol % to less than or equal to 25 mol %, from greater than or equalto 11 mol % to less than or equal to 20 mol %, from greater than orequal to 15 mol % to less than or equal to 20 mol %, or any sub-rangesformed from any of these endpoints.

The glass-based substrate may include Rb₂O in any appropriate amount. Insome embodiments, the glass-based substrate may include Rb₂O in anamount of from greater than or equal to 0 mol % to less than or equal to10 mol %, such as from greater than or equal to 1 mol % to less than orequal to 9 mol %, from greater than or equal to 2 mol % to less than orequal to 8 mol %, from greater than or equal to 3 mol % to less than orequal to 7 mol %, from greater than or equal to 4 mol % to less than orequal to 6 mol %, 5 mol %, or any sub-range formed from any of theseendpoints.

The glass-based substrate may include Cs₂O in any appropriate amount. Insome embodiments, the glass-based substrate may include Cs₂O in anamount of from greater than or equal to 0 mol % to less than or equal to10 mol %, such as from greater than or equal to 1 mol % to less than orequal to 9 mol %, from greater than or equal to 2 mol % to less than orequal to 8 mol %, from greater than or equal to 3 mol % to less than orequal to 7 mol %, from greater than or equal to 4 mol % to less than orequal to 6 mol %, 5 mol %, or any sub-range formed from any of theseendpoints.

In some embodiments, the glass-based substrate may have a compositionincluding: from greater than or equal to 45 mol % to less than or equalto 75 mol % SiO₂, from greater than or equal to 3 mol % to less than orequal to 20 mol % Al₂O₃, from greater than or equal to 6 mol % to lessthan or equal to 15 mol % P₂O₅, and from greater than or equal to 6 mol% to less than or equal to 25 mol % K₂O.

In some embodiments, the glass-based substrate may have a compositionincluding: from greater than or equal to 45 mol % to less than or equalto 75 mol % SiO₂, from greater than or equal to 3 mol % to less than orequal to 20 mol % Al₂O₃, from greater than or equal to 4 mol % to lessthan or equal to 15 mol % P₂O₅, and from greater than or equal to 11 mol% to less than or equal to 25 mol % K₂O.

In some embodiments, the glass-based substrate may have a compositionincluding: from greater than or equal to 55 mol % to less than or equalto 69 mol % SiO₂, from greater than or equal to 5 mol % to less than orequal to 15 mol % Al₂O₃, from greater than or equal to 6 mol % to lessthan or equal to 10 mol % P₂O₅, and from greater than or equal to 10 mol% to less than or equal to 20 mol % K₂O.

In some embodiments, the glass-based substrate may have a compositionincluding: from greater than or equal to 55 mol % to less than or equalto 69 mol % SiO₂, from greater than or equal to 5 mol % to less than orequal to 15 mol % Al₂O₃, from greater than or equal to 5 mol % to lessthan or equal to 10 mol % P₂O₅, and from greater than or equal to 11 mol% to less than or equal to 20 mol % K₂O.

In some embodiments, the glass-based substrate may have a compositionincluding: from greater than or equal to 58 mol % to less than or equalto 63 mol % SiO₂, from greater than or equal to 7 mol % to less than orequal to 14 mol % Al₂O₃, from greater than or equal to 7 mol % to lessthan or equal to 10 mol % P₂O₅, and from greater than or equal to 15 mol% to less than or equal to 20 mol % K₂O.

In some embodiments, the glass-based substrate may exhibit a Vickerscrack initiation threshold of greater than or equal to 5 kgf, such asgreater than or equal to 6 kgf, greater than or equal to 7 kgf, greaterthan or equal to 8 kgf, greater than or equal to 9 kgf, greater than orequal to 10 kgf, or more.

The glass-based substrate may have any appropriate geometry. In someembodiments, the glass-based substrate may have a thickness of less thanor equal to 2 mm, such as less than or equal to 1 mm, less than or equalto 900 μm, less than or equal to 800 μm, less than or equal to 700 μm,less than or equal to 600 μm, less than or equal to 500 μm, less than orequal to 400 μm, less than or equal to 300 μm, or less. In someembodiments, the glass-based substrate may have be plate or sheetshaped. In some other embodiments, the glass-based substrates may have a2.5D or 3D shape. As utilized herein, a “2.5D shape” refers to a sheetshaped article with at least one major surface being at least partiallynonplanar, and a second major surface being substantially planar. Asutilized herein, a “3D shape” refers to an article with first and secondopposing major surfaces that are at least partially nonplanar.

The glass-based articles may be produced from the glass-based substrateby exposure to water vapor under any appropriate conditions. Theexposure may be carried out in any appropriate device, such as a furnacewith relative humidity control. In some embodiments, the glass-basedsubstrates may be exposed to an environment with a relative humidity ofgreater than or equal to 75%, such as greater than or equal to 80%,greater than or equal to 85%, greater than or equal to 90%, greater thanor equal to 95%, greater than or equal to 99%, or more. In someembodiments, the glass-based substrate may be exposed to an environmentwith 100% relative humidity.

In some embodiments, the glass-based substrates may be exposed to anenvironment at a temperature of greater than or equal to 70° C., such asgreater than or equal to 75° C., greater than or equal to 80° C.,greater than or equal to 85° C., greater than or equal to 90° C.,greater than or equal to 95° C., greater than or equal to 100° C.,greater than or equal to 105° C., greater than or equal to 110° C.,greater than or equal to 115° C., greater than or equal to 120° C.,greater than or equal to 125° C., greater than or equal to 130° C.,greater than or equal to 135° C., greater than or equal to 140° C.,greater than or equal to 145° C., greater than or equal to 150° C.,greater than or equal to 155° C., greater than or equal to 160° C.,greater than or equal to 160° C., greater than or equal to 165° C.,greater than or equal to 170° C., greater than or equal to 175° C.,greater than or equal to 180° C., greater than or equal to 185° C.,greater than or equal to 190° C., greater than or equal to 195° C.,greater than or equal to 200° C., or more. In some embodiments, theglass-based substrates may be exposed to an environment at a temperaturefrom greater than or equal to 70° C. to less than or equal to 210° C.,such as from greater than or equal to 75° C. to less than or equal to205° C., from greater than or equal to 80° C. to less than or equal to200° C., from greater than or equal to 85° C. to less than or equal to195° C., from greater than or equal to 90° C. to less than or equal to190° C., from greater than or equal to 95° C. to less than or equal to185° C., from greater than or equal to 100° C. to less than or equal to180° C., from greater than or equal to 105° C. to less than or equal to175° C., from greater than or equal to 110° C. to less than or equal to170° C., from greater than or equal to 115° C. to less than or equal to165° C., from greater than or equal to 120° C. to less than or equal to160° C., from greater than or equal to 125° C. to less than or equal to155° C., from greater than or equal to 130° C. to less than or equal to150° C., from greater than or equal to 135° C. to less than or equal to145° C., 140° C., or any sub-ranges formed from these endpoints.

In some embodiments, the glass-based substrate may be exposed to thewater vapor containing environment for a time period sufficient toproduce the desired degree of hydrogen-containing species diffusion andthe desired depth of layer. In some embodiments, the glass-basedsubstrate may be exposed to the water vapor containing environment forgreater than or equal to 1 day, such as greater than or equal to 2 days,greater than or equal to 3 days, greater than or equal to 4 days,greater than or equal to 5 days, greater than or equal to 6 days,greater than or equal to 7 days, greater than or equal to 8 days,greater than or equal to 9 days, greater than or equal to 10 days,greater than or equal to 15 days, greater than or equal to 20 days,greater than or equal to 25 days, greater than or equal to 30 days,greater than or equal to 35 days, greater than or equal to 40 days,greater than or equal to 45 days, greater than or equal to 50 days,greater than or equal to 55 days, greater than or equal to 60 days,greater than or equal to 65 days, or more. In some embodiments, theglass-based substrate may be exposed to the water vapor containingenvironment for a time period from greater than or equal to 1 day toless than or equal to 70 days, such as from greater than or equal to 2days to less than or equal to 65 days, from greater than or equal to 3days to less than or equal to 60 days, from greater than or equal to 4days to less than or equal to 55 days, from greater than or equal to 5days to less than or equal to 45 days, from greater than or equal to 6days to less than or equal to 40 days, from greater than or equal to 7days to less than or equal to 35 days, from greater than or equal to 8days to less than or equal to 30 days, from greater than or equal to 9days to less than or equal to 25 days, from greater than or equal to 10days to less than or equal to 20 days, 15 days, or any sub-ranges formedfrom any of these endpoints. The exposure conditions may be modified toreduce the time necessary to produce the desired amount ofhydrogen-containing species diffusion into the glass-based substrate.For example, the temperature and/or relative humidity may be increasedto reduce the time required to achieve the desired degree ofhydrogen-containing species diffusion and depth of layer into theglass-based substrate.

The glass-based articles disclosed herein may be incorporated intoanother article such as an article with a display (or display articles)(e.g., consumer electronics, including mobile phones, tablets,computers, navigation systems, wearable devices (e.g., watches) and thelike), architectural articles, transportation articles (e.g.,automotive, trains, aircraft, sea craft, etc.), appliance articles, orany article that requires some transparency, scratch-resistance,abrasion resistance or a combination thereof. An exemplary articleincorporating any of the glass-based articles disclosed herein is shownin FIGS. 2A and 2B. Specifically, FIGS. 2A and 2B show a consumerelectronic device 200 including a housing 202 having front 204, back206, and side surfaces 208; electrical components (not shown) that areat least partially inside or entirely within the housing and includingat least a controller, a memory, and a display 210 at or adjacent to thefront surface of the housing; and a cover substrate 212 at or over thefront surface of the housing such that it is over the display. In someembodiments, at least a portion of one of the cover substrate 212 andthe housing 202 kmay include any of the glass-based articles disclosedherein.

Exemplary Embodiments

Glass compositions that are particularly suited for formation of theglass-based articles described herein were formed into glass-basedsubstrates. The compositions of Examples 1-6 are described in Table IIbelow. The density was determined using the buoyancy method of ASTMC693-93(2013). The linear coefficient of thermal expansion (CTE) overthe temperature range 25° C. to 300° C. is expressed in terms of 10⁻⁷/°C. and was determined using a push-rod dilatometer in accordance withASTME228-11. The strain point and anneal point were determined using thebeam bending viscosity method of ASTM C598-93(2013). The softening pointwas determined using the parallel plate viscosity method of ASTMC1351M-96(2012). The temperatures where the glass had a viscosity of 200P, 35,000 P, and 200,000 P were measured for the produced compositionsin accordance with ASTM C965-96(2012), titled “Standard Practice forMeasuring Viscosity of Glass Above the Softening Point.”

TABLE II Composition (mol %) Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 SiO₂60.67 60.73 60.69 61.03 61.5 61.15 Al₂O₃ 10.81 12.85 8.91 10.89 10.8910.9 P₂O₅ 9.86 7.9 11.77 9.65 9.22 9.51 K₂O 18.66 18.52 18.63 18.4318.39 18.44 Density (g/cm³) 2.375 2.385 2.362 2.375 2.376 2.376 CTE(10⁻⁷/° C.) 110.8 104.8 118.5 110 110.3 110 Strain Point (° C.) 540 596532 530 538 Anneal Point (° C.) 592 657 584 584 592 Softening Point (°C.) 892.2 959.8 885.2 888.4 902.6 892.3 200 P Temperature (° C.) 16871766 1686 35,000 P Temperature (° C.) 1219 1290 1155 200,000 PTemperature (° C.) 1112 1184 1055

A glass-based substrate including the composition of Example 1 andhaving a thickness of 1 mm was exposed to an environment of 85% relativehumidity for 65 days to form a glass-based article including ahydrogen-containing layer of the type described herein.

The depth of the hydrogen-containing layer was measured by SIMS beforeand after exposure. The result of the SIMS hydrogen concentrationmeasurement is shown in FIG. 3 , with the as-received glass-basedsubstrate hydrogen concentration curve 301 having a depth of layer ofabout 5 μm and the glass-based article hydrogen concentration curve 302having a depth of layer of about 30 μm. The post-exposure glass-basedarticle was measured to a depth of about 25 μm, and the curveextrapolated 303 to determine the depth of layer. The hydrogendiffusivity (D) was calculated based on the measured values using thegeneral formula DOL=sqrt(D·time).

The Vickers indentation cracking threshold was measured before and afterexposure to the water vapor containing environment. The result of theVickers indentation of the preexposure glass-based substrate is shown inFIGS. 4 and 5 , after indentation at 5 kgf and 10 kgf, respectively. Asshown in FIGS. 4 and 5 , the glass-based substrate had a Vickers crackinitiation threshold above 5 kgf but below 10 kgf. The result of theVickers indentation of the exposed glass-based article is shown in FIGS.6, 7, and 8 , after indentation at 5 kgf, 10 kgf, and 20 kgf,respectively. As demonstrated by FIGS. 6, 7, and 8 , the Vickersindentation cracking threshold of the glass-based article was greaterthan 20 kgf.

Glass-based substrates including compositions of Comparative Examples 1to 3 and having a thickness of 1 mm were also prepared and exposed to anenvironment of 85% relative humidity for 30 days. The compositions ofComparative Examples 1 to 3 are reported in Table III below. The Vickersindentation cracking threshold was measured before and after exposure tothe water vapor containing environment, and the depth of thehydrogen-containing layer was measured by SIMS after exposure. Thehydrogen diffusivity was calculated based on the measured values.

TABLE III Comp. Comp. Comp. Composition (mol %) Ex. 1 Ex. 1 Ex. 2 Ex. 3SiO₂ 60.67 70.05 70.43 72.44 Al₂O₃ 10.81 9.98 10 8.18 P₂O₅ 9.86 0 0 0Li₂O 0 19.97 0 0 Na₂O 0 0 19.57 0 K₂O 18.66 0 0 19.38 VickersIndentation  5-10 1-2 0.5-1 1-2 Threshold - as received (kgf) Exposuretime (days) 65 30 30 30 Hydrogen DOL (μm) 25 0.2 0.34 3.7 HydrogenDiffusivity 1.10E−12 1.30E−16 4.50E−16 5.30E−14 (cm²/s) VickersIndentation 20-30 1-2 0.5-1 2-3 Threshold - post exposure (kgf)

As shown in Table III, the glass composition of Example 1 exhibited ahydrogen diffusivity that was two orders of magnitude higher than theglass composition of Comparative Example 3, which also includedpotassium but did not include phosphorous. These results indicate thatthe presence of phosphorous in the glass composition significantlyincreases the hydrogen diffusivity. Similarly, the glass composition ofComparative Example 3 exhibited a hydrogen diffusivity that was twoorders of magnitude higher than the Comparative Examples 1 and 2, whichincluded lithium and sodium, respectively. The difference in hydrogendiffusivity between the potassium containing glass composition and thelithium and sodium containing glass compositions indicates that alkaliions with larger ionic radii allow for faster hydrogen diffusion.

Glass-based substrates including the glass composition of Example 6 wereproduced with thicknesses of 0.5 mm and 1.0 mm. The glass-basedsubstrates were exposed to a 100% relative humidity environment at atemperature of 200° C. for a period of 7 days to produce glass-basedarticles of the type described herein. The glass-based articlesexhibited a compressive stress region extending from the surface to adepth of compression. The maximum compressive stress measured for the0.5 mm glass-based article was 124 MPa, and the maximum compressivestress measured for the 1.0 mm glass-based article was 137 MPa. Themaximum central tension measured for the 0.5 mm glass-based article was32 MPa, and the maximum central tension measured for the 1.0 mmglass-based article was 15 MPa. The depth of compression for the 0.5 mmglass-based article was 101 μm, and the depth of compression for the 1.0mm glass-based article was 99 μm.

Samples were also cut from the center of the 0.5 mm and 1.0 mm thickglass-based articles formed from the glass-based substrates includingthe glass composition of Example 6 after exposure to a 100% relativehumidity environment at 200° C. for 7 days. The samples were thenpolished to a width of 0.5 mm and subjected to Fourier-transforminfrared spectroscopy (FTIR) analysis. The FTIR analysis was performedwith the following conditions: CaF/InSb, 64 scans, 16 cm⁻¹ resolution,10 μm aperture, and 10 μm steps. The scans originated at the surface ofthe samples and continued to the approximate mid-point of the thickness.The spectrums were made relative to “dry” silica, and the hydoxyl (βOH)concentration was calculated using 3900 cm⁻¹ max and 3550 cm⁻¹ minparameters. It was not possible to distinguish bound hydroxyl frommolecular hydroxyl due to the multi-component nature of the glass-basedarticle, so the plots report the concentration of the total hydroxylcontent. The measured hydroxyl concentration profiles of the 0.5 mmthick and 1.0 mm thick samples are shown in FIGS. 9 and 10 ,respectively. As shown in FIGS. 9 and 10 , the depth within the sampleswhere the measured hydroxyl content becomes substantially constant andequivalent to the hydroxyl content at the center of the articles,indicating the background hydroxyl content of the precursor glass-basedsubstrate, was approximately 200 μm as measured with FTIR. Theappearance of a buried hydroxyl concentration peak in FIGS. 9 and 10 isan artifact of the measurement method.

Square samples of with the composition of Example 1 were prepared with athickness of 1 mm and 50 mm sides. Five of these samples were thentreated in a 100% relative humidity environment at 200° C. for 121hours. The resulting compressive stress (CS) and depth of compression(DOC) of the treated samples was then measured with FSM, yielding a CSof 167 MPa and DOC of 73 μm. The 5 steam treated samples and 3 controlsamples that were not exposed to the steam treatment were then subjectedto abraded ring-on-ring (AROR) testing. The strength and peak load foreach tested sample is reported in Table IV. As shown in Table IV, thesteam treated samples exhibited a greatly increased peak load andstrength in comparison to the non-treated control samples.

TABLE IV Peak Load (kgf) Strength (MPa) Control Sample No. 1 12.46845.676 2 12.057 49.664 3 14.289 51.861 Mean 12.938 49.067 Treated SampleNo. 1 42.296 170.492 2 41.067 153.003 3 38.182 170.168 4 38.799 154.2735 38.420 150.417 Mean 39.752 159.671

The AROR test is a surface strength measurement for testing flat glassspecimens, and ASTM C1499-09(2013), entitled “Standard Test Method forMonotonic Equibiaxial Flexural Strength of Advanced Ceramics at AmbientTemperature,” serves as the basis for the AROR test methodology utilizedherein. The contents of ASTM C1499-09 are incorporated herein byreference in their entirety. The glass specimen is abraded prior toring-on-ring testing with 90 grit silicon carbide (SiC) particles thatare delivered to the glass sample using the method and apparatusdescribed in Annex A2, entitled “abrasion Procedures,” of ASTMC158-02(2012), entitled “Standard Test Methods for Strength of Glass byFlexure (Determination of Modulus of Rupture). The contents of ASTMC158-02 and the contents of Annex 2 in particular are incorporatedherein by reference in their entirety.

Prior to ring-on-ring testing a surface of the glass-based articlesamples was abraded as described in ASTM C158-02, Annex 2, to normalizeand/or control the surface defect condition of the sample using theapparatus shown in FIG. A2.1 of ASTM C158-02. The abrasive material issandblasted onto the surface of the glass-based article at an airpressure of 5 psi. After air flow is established, 1 cm³ of abrasivematerial is dumped into a funnel and the sample is sandblasted.

For the AROR test, a glass-based article having at least one abradedsurface as shown in FIG. 11 is placed between two concentric rings ofdiffering size to determine equibiaxial flexural strength (i.e., themaximum stress that a material is capable of sustaining when subjectedto flexure between two concentric rings). In the AROR configuration 400,the abraded glass-based article 410 is supported by a support ring 420having a diameter D2. A force F is applied by a load cell (not shown) tothe surface of the glass-based article by a loading ring 430 having adiameter D1.

The ratio of diameters of the loading ring and support ring D1/D2 may bein a range from 0.2 to 0.5. In some embodiments, D1/D2 is 0.5. Loadingand support rings 430, 420 should be aligned concentrically to within0.5% of support ring diameter D2. The load cell used for testing shouldbe accurate to within ±1% at any load within a selected range. Testingis carried out at a temperature of 23±2° C. and a relative humidity of40±10%.

For fixture design, the radius r of the protruding surface of theloading ring 430 is in a range of h/2≤r≤3h/2, where h is the thicknessof glass-based article 410. Loading and support rings 430, 420 are madeof hardened steel with hardness HRc>40. AROR fixtures are commerciallyavailable.

The intended failure mechanism for the AROR test is to observe fractureof the glass-based article 410 originating from the surface 430 a withinthe loading ring 430. Failures that occur outside of this region—i.e.,between the loading ring 430 and support ring 420—are omitted from dataanalysis. Due to the thinness and high strength of the glass-basedarticle 410, however, large deflections that exceed ½ of the specimenthickness h are sometimes observed. It is therefore not uncommon toobserve a high percentage of failures originating from underneath theloading ring 430. Stress cannot be accurately calculated withoutknowledge of stress development both inside and under the ring(collected via strain gauge analysis) and the origin of failure in eachspecimen. AROR testing therefore focuses on peak load at failure as themeasured response.

While typical embodiments have been set forth for the purpose ofillustration, the foregoing description should not be deemed to be alimitation on the scope of the disclosure or appended claims.Accordingly, various modifications, adaptations, and alternatives mayoccur to one skilled in the art without departing from the spirit andscope of the present disclosure or appended claims.

What is claimed is:
 1. A glass-based article, comprising: ahydrogen-containing layer extending from a surface of the glass-basedarticle to a depth of layer; a compressive stress layer extending fromthe surface of the glass-based article to a depth of compression,wherein the compressive stress layer comprises a compressive stressgreater than or equal to 100 MPa; wherein a center of the glass-basedarticle comprises: SiO₂; Al₂O₃; greater than or equal to 4 mol % to lessthan or equal to 15 mol % P₂O₅; greater than or equal to 6 mol % to lessthan or equal to 25 mol % R₂O, wherein the R₂O is the sum of alkalimetal oxides.
 2. The glass-based article of claim 1, wherein the R₂Ocomprises K₂O.
 3. The glass-based article of claim 2, wherein the K₂O isgreater than or equal to 6 mol % and less than or equal to 25 mol %. 4.The glass-based article of claim 3, wherein the R₂O is furthercomprising at least one of Na₂O, Cs₂O, and Rb₂O.
 5. The glass-basedarticle of claim 1, wherein a maximum hydrogen concentration is locatedat the surface of the glass-based article, and wherein a hydrogenconcentration of the hydrogen-containing layer decreases from themaximum hydrogen concentration to the depth of layer.
 6. The glass-basedarticle of claim 1, wherein the center of the glass-based articlecomprises: greater than or equal to 45 mol % to less than or equal to 75mol % SiO₂; greater than or equal to 3 mol % to less than or equal to 20mol % Al₂O₃; greater than or equal to 4 mol % to less than or equal to15 mol % P₂O₅; and greater than or equal to 11 mol % to less than orequal to 25 mol % R₂O.
 7. The glass-based article of claim 6, whereinthe center of the glass-based article comprises: greater than or equalto 0 mol % to less than or equal to 10 mol % Cs₂O; and greater than orequal to 0 mol % to less than or equal to 10 mol % Rb₂O.
 8. Theglass-based article of claim 7, wherein the glass-based article issubstantially free of lithium such that the lithium is less than 0.01mol %.
 9. The glass-based article of claim 1, wherein the depth ofcompression is greater than or equal to 75 μm, and wherein the depth oflayer is at greater than 5 μm.
 10. The glass-based article of claim 1,wherein the depth of compression is greater than or equal to 0.05 t,where t is thickness of the glass-based article.
 11. The glass-basedarticle of claim 10, having a thickness of less than 2 mm.
 12. Aconsumer electronic product, comprising: a housing comprising a frontsurface, a back surface and side surfaces; electrical components atleast partially within the housing, the electrical components comprisingat least a controller, a memory, and a display, the display at oradjacent the front surface of the housing; and a cover substratedisposed over the display, wherein at least a portion of at least one ofthe housing or the cover substrate comprises the glass-based article ofclaim
 11. 13. A method for manufacturing a glass-based article,comprising: exposing a glass-based substrate to water vapor and anenvironment at a temperature of greater than or equal to 70° C. to makethe glass-based article comprising a hydrogen-containing layer extendingfrom a surface of the glass-based article to a depth of layer; whereinthe environment includes a relative humidity of greater than or equal to75%; and wherein the glass-based substrate comprises SiO₂, Al₂O₃, P₂O₅,and R₂O, wherein the R₂O is the sum of alkali metal oxides.
 14. Themethod of claim 13, wherein the P₂O₅ is greater than or equal to 4 mol %to less than or equal to 15 mol % P₂O₅, and wherein the R₂O is greaterthan or equal to 6 mol % to less than or equal to 25 mol %.
 15. Themethod of claim 13, wherein the R₂O comprises K₂O, wherein the K₂O isgreater than or equal to 6 mol % and less than or equal to 25 mol %. 16.The method of claim 15, wherein the R₂O is further comprising at leastone of Na₂O, Cs₂O, and Rb₂O, and wherein the glass is substantially freeof lithium such that the lithium is less than 0.01 mol %.
 17. The methodof claim 13, wherein after the exposing, the glass-based substratecomprises a hydrogen-containing layer extending from a surface of theglass-based article to a depth of layer, wherein the depth of layer isat greater than 5 μm,
 18. The method of claim 13, wherein after theexposing, the glass-based substrate comprises a compressive stress layerextending from the surface of the glass-based article to a depth ofcompression, wherein the compressive stress layer comprises acompressive stress greater than or equal to 100 MPa.
 19. The method ofclaim 18, wherein the depth of compression is greater than or equal to75 μm, and wherein the depth of layer is at greater than 5 μm.
 20. Themethod of claim 13, wherein the depth of compression is greater than orequal to 0.05 t, where tis thickness of the glass-based article.